WO2019070587A1 - Compositions durcissables par uv ayant des propriétés mécaniques et chimiques contrôlées, procédés, et articles associés - Google Patents

Compositions durcissables par uv ayant des propriétés mécaniques et chimiques contrôlées, procédés, et articles associés Download PDF

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Publication number
WO2019070587A1
WO2019070587A1 PCT/US2018/053765 US2018053765W WO2019070587A1 WO 2019070587 A1 WO2019070587 A1 WO 2019070587A1 US 2018053765 W US2018053765 W US 2018053765W WO 2019070587 A1 WO2019070587 A1 WO 2019070587A1
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Prior art keywords
diisocyanate
composition
bis
acrylate
isocyanatomethyl
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PCT/US2018/053765
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English (en)
Inventor
Paul Share
David Chen
Stephen GODLEW
Emma COURY
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Basf Se
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Priority to KR1020207012037A priority Critical patent/KR20200056452A/ko
Priority to EP18792707.4A priority patent/EP3691901A1/fr
Priority to JP2020518474A priority patent/JP2020536142A/ja
Priority to US16/652,223 priority patent/US20200247932A1/en
Priority to CN201880063983.XA priority patent/CN111448071A/zh
Publication of WO2019070587A1 publication Critical patent/WO2019070587A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

  • the present technology is generally related to three dimensional (3D) printing technology, and, more specifically, it is related to 3D compositions for inkjet,
  • Stereolithography SLA
  • Digital Light Processing DLP
  • Oligomeric materials may be used in 3D printing compositions to achieve desirable mechanical properties to the final 3D printed object.
  • materials such as urethane acrylates typically have high viscosities that are not desirable for 3D UV inkjet, SLA, or DLP technologies.
  • the current state of the art compensates for the viscosity limitations of UV inkjet printing by using compositions having high levels (>60%) of monofunctional acrylates to achieve suitable viscosities.
  • monofunctional acrylates are not capable of crosslinking and have low reactivity compared to higher functional resins, resulting in finished articles containing significant levels of unreacted monomers, and this can lead to mechanical and chemical instability.
  • SLA, or DLP composition are not necessarily those which provide for optimal mechanical properties of the finished article. There is a need for materials that address the shortcomings of high monomer compositions with respect to incomplete cure, limited performance range, and multilayer performance degradation.
  • Another aspect of the present technology relates to an oligomer compound with one or more ethylenically unsaturated groups is provided, where the oligomer is a compound according to Formula I:
  • A is derived from one or more poly hydroxyl group compounds having a molecular weight less than about 1000 g/mol;
  • D, X, and Y are independently urethane or carbamate linkages derived from one or more polyisocyanates
  • Q and Z are independently derived from one or more compounds having at least one ethylenically unsaturated group
  • n is an integer from 1 to 20;
  • n is an integer from 0 to 20.
  • the present technology relates to a composition that includes one or more ethylenically unsaturated monomers and one or more of the oligomers, wherein the composition is a 3D UV curable composition.
  • One aspect of the present technology provides a composition including one or more ethylenically unsaturated monomers.
  • A is derived from one or more poly hydroxyl group compounds having a number average molecular weight (M n ) from about 250 to about 3000 g/mol; D, X, and Y are independently urethane or carbamate linkages derived from one or more polyisocyanates; Q and Z are independently derived from one or more compounds having at least one
  • a commercial urethane acrylates wherein the commercial urethane acrylates are derived from the group consisting of polyether, polyester, polycarbonate, alkyl or aryl polyols, alkyl or aryl polyisocyanates, hydroxyl functional (meth)acrylates, and blends of polyols and/or isocyanates; or
  • composition is a 3D UV curable composition.
  • compositions may be useful for inkjet, SLA, and/or
  • compositions described herein may have an oligomer content of at least about 55.0 wt.%.
  • the composition may include one or more photoinitiators.
  • the present technology also provides a package that includes any of the compositions described herein.
  • the present technology relates to a method for preparing a
  • the method includes applying successive layers of one or more of the compositions described herein in any embodiment to fabricate a 3D article; and irradiating the successive layers with UV irradiation.
  • the composition may be inkjet, SLA, and/or DLP deposited.
  • the present technology provides a 3D article that includes UV cured successive layers of any of the compositions described herein.
  • the compositions may be deposited by inkjet, SLA, or DLP. BRIEF DESCRIPTION OF THE DRAWINGS
  • FIGS. 1A, IB, 1C, and ID are graph illustrating the effect of oligomer content of various instant oligomer compositions on elongation properties of cured films, according to the examples.
  • FIG. IB is a graph illustrating the effect of oligomer content of various instant oligomer compositions on tensile properties of cured films, according to the examples.
  • FIG. 1C is a graph illustrating the effect of oligomer content on the elongation properties for Oligomer I (IPDI and a 590 MW polyether polyol), according to the examples.
  • FIG. ID is a graph illustrating the effect of oligomer content on the tensile properties for Oligomer I (IPDI and a 590 MW polyether polyol), according to the examples.
  • FIG. 2 is a graph illustrating the effect of photoinitiator content on modulus at
  • FIGS. 3 A, 3B, and 3C are graph illustrating the effect of soft segment (i.e., polyol) molecular weight on modulus, according to the examples.
  • FIG. 3B is a graph illustrating the relationship between modulus at 30 °C and percent elongation.
  • FIG. 3C is a graph illustrating the relationship between the elongation at break and the molecular weight of the soft segment (i.e., polyol).
  • FIG. 4 is a graph illustrating the rate of composition weight loss over time at
  • FIGS. 5A and 5B are graph illustrating the effect of curing with short and long wavelength UV irradiation on cured film modulus, according to the examples.
  • FIG. 5B is a graph illustrating the effect of film layer thickness on inkjet printed 3D UV curable compositions, according to the examples.
  • FIGS. 6A and 6B are graph illustrating the tensile strength and elongation properties of a wide range of polyol/isocyanate combinations.
  • FIG. 6B is a graph illustrating the effect of sample preparation and curing method on tensile and percent elongation. DETAILED DESCRIPTION
  • substituted refers to an alkyl, alkenyl, alkynyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms.
  • Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom.
  • a substituted group will be substituted with one or more substituents, unless otherwise specified.
  • a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents.
  • substituent groups include: halogens (i.e., F, CI, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo);
  • substituted may provide for attachment of an alkyl group to another defined group, such as a cycloalkyl group.
  • alkyl or “alkane” groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in any embodiments, from 1 to 8 carbon atoms.
  • alkyl groups include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted.
  • straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups.
  • haloalkyl is an alkyl group having one or more halo groups. In any embodiments, haloalkyl refers to a per-haloalkyl group.
  • alkyl groups may include in addition to those listed above, but are not limited to, 2-pentyl, 2-methylbutyl, 3- methylbutyl, 1,2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2- hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, l,3Dimethylbutyl, 2,3Dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3Dimethylbutyl, 1,1,2- trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, 2- heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, 2-ethylhexyl, 2-propyl,
  • Groups described herein having two or more points of attachment i.e., divalent, trivalent, or polyvalent
  • divalent alkyl groups are alkylene groups
  • divalent aryl groups are arylene groups
  • divalent heteroaryl groups are divalent heteroarylene groups, and so forth.
  • Substituted groups having a single point of attachment to the compound of the present technology are not referred to using the "ene" designation.
  • alkylene refers to a straight chain divalent alkyl group, typically having from 2 to 20 carbon atoms, or from 2 to 12 carbon atoms, or in any embodiments, from 2 to 8 carbon atoms. Alkylene groups may be substituted or
  • straight chain alkylene groups include methylene, ethylene, n- propylene, n-butylene, n-pentylene n-hexylene, n-heptylene, and n-octylene groups.
  • alkyl groups may be substituted one or more times with, for example, amino, thio, hydroxyl, cyano, alkoxy, and/or halo groups such as F, CI, Br, and I
  • alkenyl or “alkene” or “olefin” includes straight and branched chain alkyl groups as defined above, except that at least one double bond exists between two carbon atoms.
  • Alkenyl groups have from 2 to 12 carbon atoms, and typically from 2 to 10 carbons or, in any embodiments, from 2 to 8, 2 to 6, or 2 to 4 carbon atoms. In any embodiments, the alkenyl group has one, two, or three carbon-carbon double bonds.
  • alkenyl groups may be mono-substituted or substituted more than once, such as, but not limited to, mono-, di- or tri- substituted with substituents such as those listed above.
  • alkenyl alkene
  • olefin olefin
  • Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substituted or unsubstituted.
  • Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above.
  • Representative substituted cycloalkyl groups may be mono- substituted or substituted more than once, such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6- disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.
  • aryl or "aromatic,” groups are cyclic aromatic
  • Aryl groups include monocyclic, bicyclic and polycyclic ring systems.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups.
  • aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups.
  • aryl groups includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like).
  • Aryl groups may be substituted or unsubstituted.
  • (meth)acrylic or (meth)acrylate refers to acrylic or methacrylic acid, esters of acrylic or methacrylic acid, and salts, amides, and other suitable derivatives of acrylic or methacrylic acid, and mixtures thereof.
  • suitable (meth)acrylic monomers include, without limitation, the following methacrylate esters: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate (BMA), isopropyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ⁇ , ⁇ -dimethylaminoethyl methacrylate, ⁇ , ⁇ -diethylaminoethyl methacrylate, t- butylaminoethyl methacrylate, 2-sulfoethyl methacrylate, trifluoroethyl methacrylate, glycidyl methacrylate (GMA), benzyl methacrylate, allyl
  • GMA
  • methacrylate cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, hexafluoroisopropyl methacrylate, methallyl methacrylate, 3-methoxybutyl methacrylate, 2- methoxybutyl methacrylate, 2-nitro-2-methylpropyl methacrylate, n-octylmethacrylate, 2- ethylhexyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate, phenyl methacrylate, propargyl methacrylate, tetrahydrofurfuryl methacrylate and tetrahydropyranyl methacrylate.
  • Suitable acrylate esters include, without limitation, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), n-decyl acrylate, isobutyl acrylate, n-amyl acrylate, n-hexyl acrylate, isoamyl acrylate, 2- hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ⁇ , ⁇ -dimethylaminoethyl acrylate, N,N- diethylaminoethyl acrylate, t-butylaminoethyl acrylate, 2-sulfoethyl acrylate, trifluoroethyl acrylate, glycidyl acrylate, benzyl acrylate, allyl acrylate, 2-n-butoxyethyl acrylate, 2- chloroethyl acrylate
  • acrylic-containing group or “methacrylate- containing group” refers to a compound that has a polymerizable acrylate or methacrylate group.
  • Stepolithography or "SLA” refers to a form of 3D printing technology used for creating models, prototypes, patterns, and production of parts in a layer-by-layer fashion using photopolymerization, a process by which light causes chains of molecules to link, forming polymers. Those polymers then make up the body of a three- dimensional solid.
  • DLP Digital Light Processing
  • 3D printing and stereolithography 3D printing and stereolithography
  • DLP is a display device based on optical micro-electro-mechanical technology that uses a digital micromirror device.
  • DLP may use as a light source in printers to cure resins into solid 3D objects.
  • oligomer compounds for use in high oligomer UV curable compositions, high oligomer UV curable compositions, methods of using high oligomer UV curable compositions, and product compositions.
  • the high oligomer compositions can be printed using inkjet print heads or other 3D printing techniques (e.g., SLA and/or DLP), and offer enhanced formula stability during the printing process, since the monomers, which represent the most volatile components of the 3D printing composition, are substantially reduced.
  • the mechanical and chemical resistance properties of such compositions are particularly desirable in semiconductor manufacturing applications such as Chemical Mechanical Polishing (CMP), where mechanical and chemical stability and integrity of polishing pads are particularly critical. Additionally, the mechanical properties obtained can also be utilized in other applications such as conventional UV or LED printing inks and coatings, wood coatings, optical fiber coatings, laminating adhesives, and other areas in which substrate adhesion, and mechanical/chemical toughness are of interest.
  • the inventors of the technology described herein have found that the mechanical and chemical properties of a 3D printed object are controllable by combining monomer selection, temperature control, solvent addition, photoinitiator optimization, and/or oligomer structure.
  • the compositions of the present technology exhibit desirable modulus, tensile, elongation, chemical resistance, and temperature that are advantageous in various applications, including three-dimensional printed articles produced by UV inkjet, SLA, or DLP printing.
  • the present compositions exhibit enhanced mechanical and chemical properties when used in 3D printing applications over high monomer content compositions, which currently represent the state of the art.
  • the inventors have found that the curing and crosslinking properties of the compositions may be modified using non-acrylate functional materials such as thiols and siloxanes, which functionalities may also be present on the same molecule.
  • the thiols are advantageous as agents to control oxygen inhibition, which can be particularly problematic in thin films such as those generated in the 3D printing process. It was also surprisingly found that specific combinations of monomers in specific ratios yield enhanced tensile and elongation properties of the composition.
  • compositions having high oligomer levels of about 55 wt% or greater exhibit improved modulus and elongation over resins having high monomer content.
  • oligomer compounds for use in UV curable compositions, UV curable compositions, methods of using UV curable compositions, and product compositions are described herein.
  • an oligomer compound with one or more ethylenically unsaturated groups is provided, where the oligomer is a compound according to Formula I:
  • A is derived from one or more poly hydroxyl group compounds having a molecular weight less than about 1000 g/mol;
  • D, X, and Y are independently urethane or carbamate linkages derived from one or more polyisocyanates
  • Q and Z are independently derived from one or more compounds having at least one ethylenically unsaturated group
  • n is an integer from 1 to 20;
  • n is an integer from 0 to 20.
  • the present technology relates to a composition that includes one or more ethylenically unsaturated monomers and one or more of the oligomers, wherein the composition is a 3D UV curable composition.
  • composition including one or more ethylenically unsaturated monomers; and (a) one or more oligomers represented by Formula (I):
  • A is derived from one or more poly hydroxyl group compounds having a number average molecular weight (M n ) from about 250 to about 3000 g/mol;
  • D, X, and Y are independently urethane or carbamate linkages derived from one or more polyisocyanates;
  • Q and Z are independently derived from one or more compounds having at least one ethylenically unsaturated group;
  • n is an integer from 1 to 20; and m is an integer from 0 to 20;
  • a commercial urethane acrylates wherein the commercial urethane acrylates are derived from the group consisting of polyether, polyester, polycarbonate, alkyl or aryl polyols, alkyl or aryl polyisocyanates, hydroxyl functional (meth)acrylates, and blends of polyols and/or isocyanates; or
  • composition is a 3D UV curable composition.
  • the oligomer structure imparts desirable mechanical and chemical properties to the 3D UV curable compositions.
  • the structure and molecular weight of the polyol i.e., soft segment; e.g. "the di- or tri -functional alcohol-based repeat units”
  • the structure and molecular weight of the polyol may be varied for different performance attributes. It was surprisingly found that across a wide range of polyester, polycarbonate, and polyether polyols that the incorporation of a polyol having a molecular weight of about 475 g/mol or greater affected percent elongation at break.
  • FIG. 4B illustrates a near step function between a polyol having a molecular weight of 450 g/mol and a polyol having a molecular weight of 500 g/mol.
  • segment A may have a molecular weight of about less than about 1000 g/mol, in any embodiments.
  • a suitable molecular weight of the A segment includes about 200 g/mol to about 1000 g/mol, about 250 g/mol to about 900 g/mol, about 250 g/mol to about 750 g/mol, about 250 g/mol to about 500 g/mol, about 300 g/mol to about 600 g/mol, or about 500 g/mol to about 900 g/mol.
  • segment A has a molecular weight of about 250 g/mol to about 1000 g/mol.
  • segment A has a molecular weight of about 250 g/mol to about 500 g/mol.
  • segment A may have a molecular weight less than about 400 g/mol.
  • segment A may have a molecular weight of about 475 g/mol to about 3000 g/mol, about 500 g/mol to about 3000 g/mol, or about 1000 g/mol to about 3000 g/mol.
  • a suitable molecular weight of A segment includes about 475 g/mol to about 2500 g/mol, about 475 g/mol to about 2000 g/mol, about 475 g/mol to about 1500 g/mol, about 1250 g/mol to about 2900 g/mol, about 1250 g/mol to about 2750 g/mol, about 1250 g/mol to about 2500 g/mol, about 1300 g/mol to about 2300 g/mol, or about 1500 g/mol to about 2300 g/mol.
  • segment A has a molecular weight of about 1000 g/mol to about 3000 g/mol.
  • segment A has a molecular weight of about 1250 g/mol to about 2500 g/mol.
  • segment A may where R 1 and
  • R 2 may be independently derived from a diol or triol polycarbonate, a diol or triol linear Ci to Cio alkane, a diol or triol branched Ci to Cio alkane, or a Ci to Cio alkylene optionally substituted with a Ci to C 6 alkyl.
  • x may be an integer from 1 to 20. In another embodiment, x may be an integer from 1 to 10. In yet another embodiment, x may be 1, 2, 3, 4, or 5. In any embodiments of Formula I, y may be an integer from 0 to 20. In another embodiment, y may be an integer from 0 to 10. In yet another embodiment, y may be 0 or 1.
  • the A segment may be derived from polyethylene glycol, a compound of Formula (II), and/or a compound of Formula (III):
  • the A segment is derived from a compound of Formula
  • z may be an integer from 1 to 10. In another embodiment of Formula (II), z may be 1, 2, 3, 4, or 5.
  • the compound of Formula (II) has a molecular weight of less than about 400 g/mol.
  • a suitable molecular weight of Formula (II) includes about 100 g/mol to about 400 g/mol, about 150 g/mol to about 350 g/mol, about 200 g/mol to about 350 g/mol, or about 250 g/mol to about 300 g/mol.
  • the A segment is derived from a compound of Formula
  • q may be an integer from 1 to 20, or from 1 to 10. In another embodiment of Formula (III), q is 1, 2, 3, 4, or 5. In Formula (III), x may be an integer from
  • x is 1, 2 , 3, 4, or 5.
  • y may be an integer from 1 to 20. In another embodiment of Formula (III), y is 1, 2, 3, 4, or 5.
  • the A segment is derived from a compound of Formula (II) or Formula (III) may have a molecular weight of about 1000 g/mol to about 3000 g/mol, in any embodiments.
  • a suitable molecular weight of the A segment includes about 1000 g/mol to about 3000 g/mol, about 1250 g/mol to about 2900 g/mol, about 1250 g/mol to about 2750 g/mol, about 1250 g/mol to about 2500 g/mol, about 1300 g/mol to about 2300 g/mol, or about 1500 g/mol to about 2300 g/mol.
  • segment A has a molecular weight of about 1000 g/mol to about 3000 g/mol.
  • segment A has a molecular weight of about 1250 g/mol to about 2500 g/mol.
  • the A segment is derived from polyethylene glycol, a compound of Formula (II), or a compound of Formula (III).
  • the polyethylene glycol, a compound of Formula (II), or a compound of Formula (III) may have a molecular weight of about 250 g/mol to about 3000 g/mol.
  • the polyethylene glycol, a compound of Formula (II), or a compound of Formula (III) may have a molecular weight of about 475 g/mol to about 3000 g/mol, about 500 g/mol to about 3000 g/mol, or about 1000 g/mol to about 3000 g/mol.
  • a suitable molecular weight of the polyethylene glycol, a compound of Formula (II), or a compound of Formula (III) includes about 475 g/mol to about 2500 g/mol, about 475 g/mol to about 2000 g/mol, about 475 g/mol to about 1500 g/mol, about 1250 g/mol to about 2900 g/mol, about 1250 g/mol to about 2750 g/mol, about 1250 g/mol to about 2500 g/mol, about 1300 g/mol to about 2300 g/mol, or about 1500 g/mol to about 2300 g/mol.
  • the polyethylene glycol, a compound of Formula (II), or a compound of Formula (III) has a molecular weight of about 1000 g/mol to about 3000 g/mol. In another embodiment, the polyethylene glycol, a compound of Formula (II), or a compound of Formula (III) has a molecular weight of about 1250 g/mol to about 2500 g/mol. In any embodiments, the A segment is derived from polyethylene glycol.
  • the D segment may be wherein
  • D is is a substituted or unsubstituted arylene, substituted or unsubstituted cycloalkylene, or substituted or unsubstituted Ci-Ci 0 -alkylene.
  • R 3 may be a substituted or unsubstituted arylene.
  • R 3 may be a substituted or unsubstituted cycloalkylene.
  • R 3 may be a substituted or unsubstituted Ci to C 10 alkylene.
  • the X and Y segments may independently be , where R 4 is a substituted or unsubstituted arylene, substituted or unsubstituted cycloalkylene, or substituted or unsubstituted Ci-Cio-alkylene.
  • R 4 may be a substituted or unsubstituted arylene.
  • R 4 may be a substituted or unsubstituted cycloalkylene.
  • R 4 may be a substituted or unsubstituted Ci to C 10 alkylene.
  • R 3 and R 4 independently may be:
  • the D, X, and Y segments may independently be urethane or carbamate linkages derived from one or more polyisocyanates.
  • suitable polyisocyanates include, but are not limited to, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, 1,4- diisocyanatocyclohexane, 1,3- diisocyanatocyclohexane, 1,2- diisocyanatocyclohexane, 4,4'- di(isocyanatocyclohexyl)methane, 2,4'- di(isocyanatocyclohexy
  • the one or more polyisocyanates include IPDI, MDI, HMD I, and mixtures of two or more thereof.
  • m may be an integer from 0 to 20, from 0 to 10, or where m is 0 or 1.
  • the Q and Z segments may independently be derived from one or more compounds having at least one ethylenically unsaturated group.
  • suitable compounds having at least one ethylenically unsaturated group include, but are not limited to, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, glycerol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 2- hydroxyethylacrylate, 2-hydroxyethylmethacrylate, polyethylene glycol acrylate,
  • the Q and Z segments may be derived from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl vinyl ether, and mixtures of two or more thereof.
  • the oligomer may be a compound of Formula IV, a compound of Formula V, or combinations of two or more thereof.
  • the oligomer may be a commercial urethane acrylate.
  • suitable commercial urethane acrylates include, but are not limited to, urethane acrylates based on polyether, polyester, polycarbonate, alkyl or aryl polyols, aryl or alkyl polyisocyanates, hydroxyl functional (meth) acrylates, blends of such polyols and/or isocyanates, and combinations of two or more thereof.
  • compositions may include a high oligomer content, for example about 55 wt.% or greater of one or more oligomers.
  • Suitable amounts of oligomer include, but are not limited to, greater than about 55 wt.%, greater than about 60 wt.%, greater than about 65 wt.%), greater than about 70 wt.%, greater than about 75 wt.%, greater than about 80 wt.%, greater than about 85 wt.%, greater than about 90 wt.%, or a range between any two of these values.
  • the composition has an oligomer content from about 55 wt.% to about 85 wt.%), from about 60 wt.% to about 85 wt.%, or from about 75 wt.% to about 90 wt.%.
  • the one or more ethylenically unsaturated monomers are present in an amount of about 45 wt.% or less. Suitable amounts of the vinyl and/or
  • (meth)acrylate monomer include, but are not limited to, about 10 wt.% to about 45 wt.%, about 15 wt.%) to about 40 wt.%, or about 10 wt.% to about 30 wt. %.
  • the one or more ethylenically unsaturated monomers may include a vinyl and/or (meth)acrylate monomer.
  • Suitable ethylenically unsaturated monomers include, but are not limited to, (meth)acrylate monomers, (meth)acrylamide monomers, vinyl monomers, and combinations thereof.
  • suitable (meth)acrylate and (meth)acrylamide monomers include, but are not limited to, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, tert-butyl cyclohexyl (meth)acrylate, hexanediol
  • di(meth)acrylate isodecyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl(meth) acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, stearyl
  • (meth)acrylate 2-phenoxy (meth)acrylate, 2-methoxyethyl (meth)acrylate, lactone modified esters of acrylic acid, lactone modified esters of methacrylic acid, methacrylamide, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, n-hexyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl
  • (meth)acrylate glycidyl (meth)acrylate, (meth)acrylated methylolmelamine, 2-(N,N- diethylamino)-ethyl (meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, phen
  • Suitable vinyl monomers include, but are not limited to, N-vinylformamide
  • NVF adducts of NVF having diisocyanates such as toluene diisocyanate and isophorone diisocyanate (IPDI), derivatives of N-vinylformamide, N-vinylcaprolactam, N- vinylpyrrolidone, butyl-vinylether, 1,4-butyl-divinylether, dipropyleneglycol-divinylether, triallylisocyanurate, diallylphthalate, and vinyl esters of acetic acid, lauryl acid, dodecanoic acid, cyclohexylcarboxylic acid, adipic acid, glutaric acid and the like.
  • diisocyanates such as toluene diisocyanate and isophorone diisocyanate (IPDI)
  • IPDI isophorone diisocyanate
  • acetic acid lauryl acid
  • dodecanoic acid cyclohexylcarboxylic acid
  • compositions may include one or more photoinitiators.
  • Suitable photoinitiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoylphenyl phosphinate, bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, alpha- hydroxy cyclohexyl phenyl ketone, 2-hydroxy-l-(4-(4-(2-hydroxy-2- methylpropionyl)benzyl)phenyl-2-methylpropan- 1 -one, 2-hydroxy-2-methyl- 1 - phenylpropanone, 2-hydroxy-2-methyl-l-(4-isopropylphenyl)propanone, oligo (2-hydroxy-2- m ethyl- 1 -(4-( 1 -(
  • the one or more photoinitiators may be present in an amount of about 0.01 wt.% to about 6.0 wt.% of the total weight of the composition. Suitable amounts of the photoinitiator include, but are not limited to, about 0.01 wt.% to about 6.0 wt.%, about 0.1 wt.% to about 4.0 wt.%, about 0.20 wt.% to about 2.0 wt.%, or about 0.5 wt.%) to about 1.0 wt.%). In one embodiment, the photoinitiator is present in an amount from 0.25 wt.%) to about 2.0 wt.%>. In another embodiment, the photoinitiator is present in an amount from 0.5 wt.%> to about 1.0 wt.%>.
  • the viscosity of the compositions may also be controlled. It may be useful to control the viscosity of the compositions at temperatures commonly used in various printing and other applications, such as 3D inkjet, SLA, and/or DLP printing. For applications such as jetting, the composition typically has a viscosity of about 35 mPa s or less.
  • Suitable viscosities include, but are not limited to, about 35 mPa s, about 30 mPa s, about 25 mPa s, about 20 mPa s, about 18 mPa s, about 15 mPa s, about 12 mPa s, about 10 mPa s, or values between any two of these values or less than any one of these values.
  • the composition has a viscosity from about 10 mPa s to about 35 mPa s, about 10 mPa s to about 20 mPa s, or about 10 mPa s to about 15 mPa s.
  • the composition exhibits a viscosity of 35 mPa- s or less at temperatures in the range of about 25 °C to about 130 °C. In another embodiment, the viscosity is from about 10 mPa s to about 20 mPa s at a temperature from about 25 °C to about 130 °C.
  • the viscosity may be significantly higher, typically from about 100 mPas to 10,000 mPas at 25 °C (including about 500 mPas to 9,000 mPas, about 1000 mPas to 8,000 mPas, about 2000 mPas to 7,000 mPas, about 3000 mPas to 6,000 mPas, about 4000 mPas to 5,000 mPas, about 100 mPas to 5,000 mPas, about 200 mPas to 3,000 mPas, about 300 mPas to 1,000 mPas, about 5,000 mPas to 10,000 mPas, or about 7,000 mPas to 9,000 mPas).
  • the compositions may further include a solvent.
  • Suitable solvents include, but are not limited to, propylene glycol monomethyl ether acetate, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol n-butyl ether, propylene glycol diacetate, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol dimethyl ether, and mixtures of two or more thereof.
  • the compositions may further include nanoparticles.
  • Suitable nanoparticles include, but are not limited to, organocation-modified phyllosilicates, Ti0 2 , ZnO, Ag, Si0 2 , Fe 3 0 4 , CaC0 3 , A1 2 0 3 , Mg(OH) 2 , Al(OH) 3 , Ce0 2 , Mn0 2 , cellulose, graphene, carbon fiber, carbon nanotube, cloisite, montmorillonite, hectorite, saponite, or the like and mixtures of two or more thereof.
  • the nanoparticle may be an organocation-modified phyllosilicate.
  • the organocation-modified phyllosilicate is alkylammonium cation exchanged montmorillonite.
  • compositions may further include performance modifiers.
  • Suitable performance modifiers include, but are not limited to, thiols, silyl acrylates, and thiol -functional silanes.
  • the performance modifier is a thiol.
  • suitable thiols include, but are not limited to, 1-pentanethiol, 1- hexanethiol, 1-heptanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1- hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, eicosanethiol, docosanethiol, tetracosanethiol, hexacosanethiol, octacosanethiol, t-dodecyl mercaptan, methyl
  • thioglycolate methyl-3-mercaptopropionate, ethyl thioglycolate, butyl thioglycolate, butyl-3- mercaptopropionate, isooctyl thioglycolate, isooctyl-3-mercaptopropionate, isodecyl thioglycolate, isodecyl-3-mercaptopropionate, dodecyl thioglycolate, dodecyl-3- mercaptopropionate, octadecyl thioglycolate, octadecyl-3-mercaptopropionate, thiogly colic acid, 3-mercaptopropionic acid, and mixtures of two or more thereof.
  • the performance modifier may be a thio-functional silane.
  • suitable thio-functional silanes include, but are not limited, bis(3- triethoxysilylpropyl)-tetrasulfide, gamma-mercaptopropyltimethoxysilane, gamma- mercaptopropyl-triethoxysilane, and mixtures of two or more thereof.
  • compositions of the present technology may further include reaction products obtained from reacting one or more polyisocyanates and one or more compounds having at least one ethylenically unsaturated group.
  • the composition may further include a compound of Formula (VI):
  • R 20 and R 21 are independently comprise a (meth)acrylate moiety derived from one or more compounds comprising at least one ethylenically unsaturated group; and J is a divalent urethane compound derived from one or more polyisocyanates.
  • the (meth)acrylate moiety may be derived from one or more compounds having at least one ethylenically unsaturated group.
  • Suitable compounds having at least one ethylenically unsaturated group include, but are not limited to, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, glycerol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 2- hydroxyethylacrylate, 2-hydroxyethylmethacrylate, polyethylene glycol acrylate,
  • trimethyolpropane diacrylate trimethyolpropane dimethacrylate
  • pentaerythritol triacrylate pentaerythritol trimethacrylate, and mixtures of two or more thereof.
  • the divalent urethane compound may be derived from one or more polyisocyanates.
  • Suitable polyisocyanates include, but are not limited to, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,
  • MDI diisocyanate
  • HMDI 4,4'-bis-(isocyanatocyclohexyl)-methane
  • 1,2-bis- (isocyanatomethyl)-cyclobutane 1,3- and l,4-bis-(isocyanatomethyl)-cyclohexane
  • hexahydro-2,4- diisocyanatotoluene hexahydro-2,6-diisocyanatotoluene
  • bis- isocyanatom ethyl norbornane 2,5- bis-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis- (isocyanatomethyl)-bicyclo[2.2.1]heptane, l-isocyanato
  • the composition may further include ethylenically functional or non-functional non-urethane oligomers, which may further enhance the mechanical and chemical properties of the composition of the present technology.
  • Suitable non-urethane oligomers include, but are not limited to, epoxy, ethoxylated or propoxylated epoxy resins, polyesters, polyethers, polyesters, polyketones, and mixtures of two or more thereof.
  • a process for preparing an oligomer as described herein in any embodiment includes reacting one or more polyisocyanates with one or more compounds having at least one ethylenically unsaturated group and one or more poly hydroxyl group compounds, where the process is carried out thermally or in the presence of a catalyst.
  • the process may include reacting the one or more polyisocyanates with the one or more compounds having at least one ethylenically unsaturated group to form an ethylene-isocyanate intermediate having urethane bound ethylenically unsaturated groups and unreacted isocyanate groups. In any embodiments, the process further includes reacting the urethane-isocyanate intermediate with the one or more poly hydroxyl group compounds.
  • the process may include reacting the one or more polyisocyanates with the one or more poly hydroxyl group compounds to form a poly hydroxyl-isocyanate intermediate having a urethane bound poly hydroxyl group compound and unreacted isocyanate groups.
  • the poly hydroxyl-isocyanate intermediate includes hydroxyl groups of the bound poly hydroxyl groups that have reacted and isocyanate groups that are unreacted.
  • the process further includes reacting the poly hydroxyl-isocyanate intermediate with the one or more compounds having at least one ethylenically unsaturated compounds.
  • the process includes reacting the one or more polyisocyanates, one or more compounds having at least one ethylenically unsaturated group, and one or more poly hydroxyl group compounds in one reaction step.
  • the process includes the one or more polyisocyanates, poly hydroxyl group compounds, and the one or more compounds comprising at least one ethylenically unsaturated group as described herein.
  • the process may be carried out thermally or in the presence of a catalyst.
  • the process is carried out thermally.
  • the process is carried under thermal conditions suitable for polymerization.
  • the process is carried out in the presence of a catalyst.
  • suitable catalysts include, but are not limited to, organozinc, tetraalkylammonium, or organotin compounds.
  • the catalyst is an organozinc compound.
  • suitable organozinc compounds include, but are not limited to, zinc acetylacetonate, zinc 2- ethylcaproate, and the like.
  • the catalyst is a tetraalkylammonium compound.
  • suitable tetraalkylammonium compounds include, but are not limited to, N,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide, N,N,N-trimethyl-N-2- hydroxypropylammonium 2-ethylhexanoate, and the like.
  • the catalyst is an organotin compound.
  • suitable organotin compounds include, but are not limited to, dibutyltin dilaurate.
  • the process may be carried out at a temperature of about 25 °C to about 100 °C.
  • suitable temperatures include, but are not limited to, about 25 °C to about 100 °C, about 25 °C to about 75 °C, about 25 °C to about 50 °C, or about 50 °C to about 100 °C.
  • a method is provided for preparing a 3D article using any of the compositions described in any embodiment herein. The method includes applying successive layers of one or more of the compositions described herein in any embodiment to fabricate a 3D article; and irradiating the successive layers with UV irradiation.
  • Applying the composition to obtain the three-dimensional article may include depositing the composition.
  • the application may include depositing a first layer of the composition and second layer of the composition to the first layer and successive layers thereafter to obtain a 3D article.
  • Such depositing may include one or more methods, including but not limited to, UV inkjet printing, SLA, continuous liquid interface production (CLIP), and DLP.
  • Other applications for the compositions include, but are not limited to, other coating and ink applications for printing, packaging, automotive, furniture, optical fiber, and electronics.
  • the methods described herein include contacting the layers of the composition with ultraviolet light irradiation to induce curing of the composition.
  • the contacting includes short wavelength and long wavelength ultraviolet light irradiation.
  • Suitable short wavelength ultraviolet light irradiation includes UV-C or UV-B irradiation.
  • the short wavelength ultraviolet light irradiation is UV-C light.
  • Suitable longwave ultraviolet light irradiation includes UV-A irradiation.
  • Electron Beam (EB) irradiation may be utilized to induce curing of the composition.
  • the methods described herein include repeating the deposition of layers of the composition and exposure to UV irradiation to obtain the 3D article.
  • the repeating may occur sequentially wherein depositing the layers of composition is repeated to obtain the 3D article prior to exposure to UV irradiation.
  • the repeating may occur subsequently wherein the deposing the layers of composition and exposure to UV irradiation are repeated after both steps.
  • a 3D article that includes UV cured successive layers of the any of the compositions as described herein.
  • the composition may have been inkjet, SLA, or DLP deposited.
  • the 3D article may include a polishing pad.
  • polishing pad is a chemical mechanical polishing (CMP) pad. Polishing pads may be made following any known methods, for example the methods provided in U.S. Patent Appl. No. 2016/0107381, U.S. Patent Appl. No. 2016/0101500, and U.S. Patent No. 10,029,405 (each incorporated herein by reference).
  • the 3D article of the present technology exhibits improved tensile strength, modulus, and elongation properties.
  • the three-dimensional article exhibits a tensile strength of about 500 psi to about 10,000 psi.
  • the three- dimensional article may exhibit a tensile strength, including but not limited to, about 500 psi to about 10,000 psi, about 1,000 psi to about 7,500 psi, about 2,500 psi to about 6,000 psi, or about 3,000 psi to about 5,000 psi.
  • the 3D article has a modulus of about 500 MPa to about
  • the 3D article may exhibit a modulus, including but not limited to, about 500 MPa to about 10,000 MPa, about 1,000 MPa to about 7,500 MPa, about 2,500 MPa to about 6,000 MPa, or about 3,000 MPa to about 5,000 MPa.
  • the 3D article of the present technology may exhibit improved elongation properties while maintaining its tensile strength and modulus.
  • the 3D article exhibits an elongation of about 5% to about 300%.
  • the 3D article may exhibit an elongation, including but not limited to, about 5% to about 300%, about 5% to about 250%, about 5% to about 200%, about 5% to about 150%, about 5% to about 100%, about 5% to about 50%, or about 5% to about 35%.
  • IBOA isobornyl acrylate
  • NVC n-vinyl caprolactam
  • POEA phenoxyethyl acrylate
  • HDDA hexanediol diacrylate
  • DVE-3 tri ethylene glycol divinyl ether
  • TPGDA tripropyleneglycol diacrylate
  • DPGDA dipropylene glycol diacrylate
  • PPTTA ethoxylated pentaerythritol tetraacrylate
  • TBCH 4-tert-butyl cyclohexyl acrylate
  • TPO diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
  • PolyTHF ® 250 polytetramethylene glycol based polyether diol having a molecular weight of about 225 g/mol to about 275 g/mol, available from BASF SE.
  • OH groups hydroxyethyl acrylate (158.74 g, 1.22 moles), ethyl acetate (298.65 g; 3.39 mol), hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced into a 1.5 L kettle style reactor with nitrogen inlet and condenser at room temperature.
  • the temperature was increased to 35 °C, and isophorone diisocyanate (338.11 g; 1.52 mol) was added dropwise with concomitant heating to maintain a temperature of 75 °C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78 °C.
  • the reaction contents were then heated at 75 °C for five hours, during which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.6%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.60%, an equivalent amount of methanol was added, calculated relative to residual NCO, and the reaction was continued until the NCO value was ⁇ 0.12%.
  • the resulting product was analyzed by gel permeation chromatography and determined to have a number average molecular weight of (M n ) 846 g/mol and weight average molecular weight (M w ) 1922 g/mol. The product was allowed to cool and was discharged.
  • Oligomers B, C, D E, and F were prepared according to following procedures and are represented according to Formula (V).
  • Oligomer B A polycarbonate diol (Polyol C- 590R, 300.91 g, about 0.60 mol, about 1.20 mol of OH groups), hydroxyethyl acrylate (125.61 g, 0.97 mol), ethyl acetate (300.77 g), hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced to a 1.5 L kettle style reactor with a nitrogen inlet and condenser.
  • the temperature was increased to 35 °C, and isophorone diisocyanate (267.54 g, 1.20 mol) was added dropwise with concomitant heating to maintain a temperature of 75 °C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78 °C.
  • the reaction contents were then heated at 75 °C for five hours at which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.6%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.60%, an equivalent amount of methanol was added, calculated relative to residual NCO, and the reaction was continued until the NCO value was ⁇ 0.12%.
  • the resulting product was analyzed by gel permeation chromatography and determined to have M n of 1174 g/mol and M w of g/mol. The product was allowed to cool and was discharged.
  • Oligomer C 420.5 g of a polycarbonate diol (Polyol C-1090, about 0.42 mol, about 0.84 mol of OH groups), 87.7 g of hydroxyethyl acrylate (0.76 mol), 301.4 g of ethyl acetate, hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced into a 1.5 L kettle-style reactor with nitrogen inlet and condenser.
  • the temperature is increased to 35 °C, and 186.8 g (0.84 moles) of isophorone diisocyanate were added dropwise with concomitant heating to maintain a temperature of 75 °C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78 °C.
  • the reaction contents were then heated at 75 °C for 5 h at which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.4%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.40%, the equivalent amount of methanol was added, calculated relative to residual NCO, and reaction was continued until the NCO value was ⁇ 0.12%.
  • Oligomer D 527.18 g of a polycarbonate diol (Polyol C-2090, about 0.26 mol, about 0.52 mol of OH groups), 54.99 g of hydroxy ethyl acrylate (0.47 mol), 298.45 g of ethyl acetate (about 3.39 mol), hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced into a 1.5 L kettle-style reactor with nitrogen inlet and condenser.
  • the temperature was increased to 35 °C, and 1 17.12 g (0.53 mol) of isophorone diisocyanate were added dropwise with concomitant heating to maintain a temperature of 75 °C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78 °C.
  • the reaction contents were then heated at 75 °C for 5 h at which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.4%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.40%, the equivalent amount of methanol was added, calculated relative to residual NCO, and reaction was continued until the NCO value was ⁇ 0.12%.
  • the resulting product was analyzed by gel permeation chromatography and determined to have M n equal to 2,482 g/mol and M w equal to 1 1,527 g/mol. The product was allowed to cool and was discharged.
  • Oligomer E 527.18 g of a polycarbonate diol (Polyol C-2050R, about 0.26 moles, about 0.52 moles of OH groups), 54.99 g of hydroxy ethyl acrylate (0.47 mol), 298.45 g of ethyl acetate (about 3.39 mol), hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced into a 1.5 L kettle-style reactor with nitrogen inlet and condenser.
  • a polycarbonate diol Polyol C-2050R, about 0.26 moles, about 0.52 moles of OH groups
  • the temperature was increased to 35 °C, and 1 17.12 g (0.53 mol) of isophorone diisocyanate were added dropwise with concomitant heating to maintain a temperature of 75 °C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78 °C.
  • the reaction contents were then heated at 75 °C for 5 h at which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.4%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.40%), the equivalent amount of methanol was added, calculated relative to residual NCO, and reaction was continued until the NCO value was ⁇ 0.12%.
  • Oligomer F 561.32 g of a polycarbonate diol (Polyol C-3090R, about 0.19 mol, about 0.38 mol of OH groups), 43.56 g of hydroxy ethyl acrylate (0.38 mol), 300.53 g of ethyl acetate (3.41 mol), hydroquinone methyl ether (0.050 g; 0.4 mmol), butylated hydroxytoluene (1.0 g; 4.5 mmol), phenothiazine (0.1 g; 0.5 mmol), and a zinc neodecanoate catalyst (1.0 g, 2.45 mmol) were introduced into a 1.5 L kettle-style reactor with nitrogen inlet and condenser.
  • the temperature was increased to 35 °C, and 92.79 g (0.42 mol) of isophorone diisocyanate were added dropwise with concomitant heating to maintain a temperature of 75 ° C. Addition of the isocyanate was temporarily ceased if the temperature exceeded 78° C.
  • the reaction contents were then heated at 75 °C for 5 h at which time the NCO value was reduced to ⁇ 0.6%. If the NCO value was > 0.4%, then 2 g of catalyst were added and heating was continued. If the NCO value was between 0.12% and 0.40%, the equivalent amount of methanol was added, calculated relative to residual NCO, and the reaction was continued until the NCO value was ⁇ 0.12%.
  • the resulting product was analyzed by gel permeation chromatography and determined to have M n equal to 2,596 g/mol and M w equal to 14,055 g/mol. The product was allowed to cool and was discharged.
  • Oligomer G According to the synthetic procedure described is Oligomer A, the isocyanate was changed from IPDI to HMD! The resulting product was analyzed by gel permeation chromatography and determined to have M n equal to 1206 g/mol and M w equal to 2721 g/mol.
  • Oligomer H According to the synthetic procedure described is Oligomer A, the polyol was changed from polyTHF to polyethylene glycol with a molecular weight of 600 g/mol. The resulting product was analyzed by gel permeation chromatography and determined to have M n equal to 2280 g/mol and M w equal to 3424 g/mol.
  • Oligomer I According to the synthetic procedure described is Oligomer A, the polyol was changed from polyTHF with a 250 molecular weight to a polyethylene oxide with a molecular weight of 590 g/mol . The resulting product was analyzed by gel permeation chromatography and determined to have M n equal to 1710 g/mol and M w equal to 3308 g/mol. [0097] Oligomer 1. Oligomer 1 was prepared according to US 2007/0066704
  • Example 1 70 g by weight of Oligomer 1 was added to 30 g of trimethylolpropane formal aery late.
  • Oligomer 2 was prepared according to WO 2016/089271
  • oligomer 2 has an about 500 g/mol to about 1000 g/mol polyol segment. 70 g by weight of Oligomer 2 was added to 30 g of trimethylolpropane formal acrylate.
  • Example 2 Compositions.
  • compositions containing Oligomers 1 and 2 were prepared according to Table 1.
  • compositions 2 and 3 Compositions 2 and 3, respectively.
  • the compositions were prepared by blending isobornyl acrylate (IBOA)(Sigma-Aldrich), n-vinyl caprolactam (NVC), phenoxyethyl acrylate (POEA), hexanediol diacrylate (HDD A), and 4-tert-butyl cyclohexyl acrylate (TBCH) with Oligomer 1 or Oligomer 2.
  • Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) was added as a photoinitiator in a range from 0.5 to 4 wt.% to provide Compositions 2 and 3.
  • compositions 2 and 3 were formulated to contain 80-83.5 wt.% of Oligomer 1 and Oligomer 2, respectively, by removing an appropriate amount of solvent by vacuum distillation.
  • NVC, POEA, HDDA, TBCH, and TPO were obtained from BASF
  • Composition 1 was obtained following a similar procedure as above by blending a combination of Oligomer A as prepared in Example 1 with IBOA and NVC. Oligomer A was also a blend of 70 wt.% of the oligomer and 30 wt.% ethyl acetate. The product was blended with the monomers and the ethyl acetate was removed from the mixture by vacuum distillation. Like Compositions 2 and 3, Composition 1 was formulated to contain 80-83.5 wt.%) of Oligomer A by removing an appropriate amount of ethyl acetate by vacuum distillation.
  • Composition 4 (high monomer content) was obtained by diluting Composition
  • composition 2 to a 40 wt.% blend and adding the monomers POEA, HDDA, and TBCH.
  • the 40 wt.% dilution of Composition 2 corresponds to 32 wt.%> Oligomer 1, 4.8 wt.%> NVC, 1.6 wt.%> IBOA, and a portion of the TPO. Additional TPO was added to maintain a 4 wt.%> content. TABLE 1.
  • Composition 5 An oligomer blend was prepared from 70 g of Oligomer 2 and
  • composition 30 parts t-butyl cyclohexyl acrylate.
  • the following composition was prepared from the oligomer blend (40 g), NVC (6 g), IBOA (2 g), TPO (2 g), and 50 g of one or more of the following monomers: NVC, DVE-3, IBOA, TBCH, POEA, HDDA, TPGDA, DPGDA, or PPTTA.
  • composition 6 An oligomer blend was prepared from 70 g of Oligomer 2 and
  • the following composition was prepared by combining the oligomer blend (40 g), NVC (6 g), IBOA (2 g), TPO (2 g), and 50 g of one or more of the following monomers: NVC, DVE-3, IBOA, TBCH, POEA, HDDA, TPGDA, DPGDA, or PPTTA.
  • composition 7 The following composition was prepared by combining
  • Oligomer 1 (32 g), NVC (4.8 g), IBOA (1.6 g), TPO (1.6 g), and 60 g of one or more of the following monomers: NVC, DVE-3, IBOA, TBCH, POEA, HDDA, TPGDA, DPGDA, or PPTTA.
  • compositions 8-12 were prepared according to the procedure described for
  • FIG. 1C shows the effect of oligomer content on the elongation properties of an oligomer based on IPDI and a 590 MW polyether polyol (Oligomer I).
  • Figures ID shows the specific example of the effect of oligomer content on the tensile properties of Oligomer I. The data from FIGS. 1C and ID were used to create FIGS. 1 A and IB, respectively.
  • FIG. 1 A shows the elongation properties of a large number of
  • FIG. IB shows the tensile properties of a large number of monomer/oligomer combinations over a wide range of oligomer levels in the composition. Each point represents a single tensile/elongation measurement of a single composition. In contrast, to FIG. 1 A shows the effect of increasing weight percent oligomer on tensile values. The mean value of the maximum tensile strength is relatively constant at 35 weight percent oligomer and above.
  • High oligomer composition film samples according to Composition 3 were prepared having one or more layers, where each layer was about 63.5 micron thick.
  • the amount of photoinitiator in each composition was varied from 0.5 wt.%, 1 wt.%, and 2 wt.%.
  • the films were made by coating on Q-lab (Ohio, United States) 3" x 6" Q-panel aluminum test substrates. Films with multiple layers were prepared by initially coating the composition directly onto a Q-panel using 63.5 ⁇ K Hand Coater and applying subsequent layers on top.
  • the films were characterized through dynamic mechanical analysis (DMA) and tensile testing (stress/strain) measurements, both performed on a TA DMA Q800 using the film tension mode. DMA measurements were taken by equilibrating at 15 °C, then ramping the temperature to 95 °C at a rate of 5 °C/min.
  • FIG. 2 illustrates that there was an increase in modulus with the increase in the number layers.
  • the photoinitiator amount increases to 2 wt.%, the modulus decreases with increasing number of layers. Effect of oligomer structure soft segment on modulus
  • compositions 8-12 directly onto the Q-panel using the 63.5 ⁇ K Hand Coater and applying subsequent layers on top. Each sample was cured using the settings described above after each layer of the composition was applied until the desired number of layers had been deposited.
  • Table 3 corresponds to the compositions in FIG. 3 A.
  • FIG. 3 A shows that compositions containing oligomers with a polyol segment ⁇ i.e., soft segment) molecular weight of less than about 1000 g/mol exhibited higher modulus. In contrast, compositions containing oligomers with polyol segment greater than 1000 g/mol exhibited a lower modulus.
  • FIG. 3B shows that the modulus is essentially invariant up to an elongation of approximately 10%, and then sharply decreases by an order of magnitude at elongations greater than 10%.
  • FIG. 3C shows that the onset effect of polyol segment molecular weight on elongation at break is quite significant across a wide range of polyol and isocyanate types. Below a molecular weight of 500 g/mol, there are no compositions with an elongation higher than 15%), but at a molecular weight of 500 g/mol and above the maximum elongation increases to 50% and higher.
  • Composition 2 was evaluated to determine the rate of weight loss when subjected to a temperature of 70 °C over an extended period of time. Comparative evaluation was performed using a low viscosity, high monomer composition of isobornyl acrylate.
  • thermogravimetric analysis (TGA) measurements were performed using a TA Instruments (Delaware, United States) TGA Q50 analyzer. TGA data were measured using a balance purge of 10 mL/min and a sample purge of 90 mL/min. Approximately 15 mg of the sample was placed in a platinum TGA pan, and the sample was heated isothermally for 1 hour.
  • FIG. 4 illustrates a significant portion of the high monomer content was lost through volatilization.
  • Composition 2 according to present technology exhibited a significantly lower rate of weight loss, which demonstrates that the composition of the present technology which would actually emerge from the printhead does not differ over time from the initial composition.
  • the high monomer composition would emerge as a substantially different composition on the platen substrate, which would be expected to cause time-dependent changes in material properties of the 3D object.
  • a 63.5 micron thick film sample according to Composition 2 was cured following the UV curing process described above.
  • the film sample was subsequently irradiated at 390 nm for 2 seconds at a peak temperature of about 60 °C.
  • the post curing resulted in a 30% increase in the modulus at 25 °C.
  • the basis for this approach is shown in Figure 5B.
  • FIG. 5B illustrates the effect layer thickness of inkjet printed compositions according to Composition 2 on %-transmission of light at short wavelength (246 nm, 250 nm, 254 nm) and long wavelength (332 nm, 333 nm, and 390 nm), respectively.
  • Composition 2 is based on a 4 wt.% photoinitiator amount of either TPO, 1-hydroxy-cyclohexyl-phenyl-ketone (available from Ciba, Irgacure 184), and a 1 : 1 mixture of 1-hydroxy-cyclohexyl-phenyl- ketone and benzophenone (mixture available from Ciba, Irgacure 500), respectively.
  • the transmission of Irgacure 500 and Irgacure 184 in the region of 254 nm at a print layer thickness of 15-30 ⁇ has a transmission of approximately 10 "5 .
  • TPO in contrast, has a transmission 5 orders of magnitude higher over the same range of layer thicknesses, leading to a more homogeneous cure.
  • FIG. 6 A illustrates the effect of the specific polyol structures and molecular weights shown in FIGS. 1 A, IB, 3B, and 3C on tensile strength, elongation, and modulus.
  • the oligomers were formulated as a 60:40 blend of oligomer: acryloyl morpholine
  • ACMO Advanced Chemical Vapor Deposition
  • TPO-L 1% TPO-L added as photoinitiator
  • FIG. 6 A and Table 4 modifying the polyol molecular weight and isocyanate structure affect the mechanical properties.
  • the polyol molecular weight has the most significant effect on mechanical properties.
  • the numbers next to each data point in FIG. 6A indicates the Young's modulus (MPa).
  • MPa Young's modulus
  • elongation and the choice of isocyanate can have a dominant effect on tensile strength.
  • the IPDI and HMDI urethane acrylates based on pTHF having a molecular weight of 250 g/mol have the same elongation, but the use of HMDI yields approximately half the tensile strength and modulus of the IPDI based analog.
  • Figure 6 A shows that the tensile strength and elongation properties of a wide range of polyol/isocyanate combinations.
  • the mechanical properties resulting from the specific combination of polyol and isocyanate can be adjusted to meet the requirements of desired end use application properties through careful selection of the structure and molecular weight of the polyol and the isocyanate.
  • the properties achieved from a combination of 250 MW poly-THF and isophorone diisocyanate would be of interest.
  • a higher molecular weight polyol such as a polycarbonate polyol would be of interest.
  • FIG. 6B illustrates the effect of sample preparation and curing method on tensile and percent elongation.
  • the samples consist of blends of urethane acrylates based on the 1000 MW and 2000 MW polycarbonates shown in Fig 6 A.
  • DLP printed samples printed
  • the postcuring was carried out using the methodology illustrated in FIG. 5 A.

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Abstract

L'invention concerne une composition comprenant un ou plusieurs monomères à insaturation éthylénique et (a) un ou plusieurs oligomères représentés par la formule (I) : dans laquelle : A est dérivé d'un ou de plusieurs composés du groupe polyhydroxylé ayant un poids moléculaire moyen en nombre (Mn) d'environ 250 à environ 3 000 g/mol ; D, X et Y sont indépendamment des liaisons uréthane ou carbamate dérivées d'un ou plusieurs polyisocyanates ; Q et Z sont indépendamment dérivés d'un ou de plusieurs composés ayant au moins un groupe à insaturation éthylénique ; n est un nombre entier de 1 à 20 ; et m est un nombre entier de 0 à 20 ; ou (b) un ou plusieurs acrylates d'uréthane commerciaux ; ou (c) une combinaison de (a) et (b) ; la composition étant une composition durcissable aux UV 3D.
PCT/US2018/053765 2017-10-02 2018-10-01 Compositions durcissables par uv ayant des propriétés mécaniques et chimiques contrôlées, procédés, et articles associés WO2019070587A1 (fr)

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CN111448071A (zh) 2020-07-24
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